EP0065122B1 - Vorrichtungsteil aus Siliziumnitrid zum Ziehen von einkristallinem Silizium und Verfahren zu seiner Herstellung - Google Patents
Vorrichtungsteil aus Siliziumnitrid zum Ziehen von einkristallinem Silizium und Verfahren zu seiner Herstellung Download PDFInfo
- Publication number
- EP0065122B1 EP0065122B1 EP82103457A EP82103457A EP0065122B1 EP 0065122 B1 EP0065122 B1 EP 0065122B1 EP 82103457 A EP82103457 A EP 82103457A EP 82103457 A EP82103457 A EP 82103457A EP 0065122 B1 EP0065122 B1 EP 0065122B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silicon
- silicon nitride
- base member
- ppm
- nitride layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims description 202
- 229910052710 silicon Inorganic materials 0.000 title claims description 199
- 239000010703 silicon Substances 0.000 title claims description 199
- 229910052581 Si3N4 Inorganic materials 0.000 title claims description 176
- 239000013078 crystal Substances 0.000 title claims description 116
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 208
- 238000000034 method Methods 0.000 claims description 52
- 230000008021 deposition Effects 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 39
- 239000012071 phase Substances 0.000 claims description 37
- 230000003746 surface roughness Effects 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000012535 impurity Substances 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 239000007792 gaseous phase Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 description 104
- 239000007789 gas Substances 0.000 description 56
- 239000010408 film Substances 0.000 description 54
- 238000000151 deposition Methods 0.000 description 49
- 238000005229 chemical vapour deposition Methods 0.000 description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 13
- 239000010409 thin film Substances 0.000 description 13
- 238000000465 moulding Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011863 silicon-based powder Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000008646 thermal stress Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000001546 nitrifying effect Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910003910 SiCl4 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000019592 roughness Nutrition 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910010066 TiC14 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/10—Crucibles or containers for supporting the melt
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/20—Controlling or regulating
- C30B15/22—Stabilisation or shape controlling of the molten zone near the pulled crystal; Controlling the section of the crystal
- C30B15/24—Stabilisation or shape controlling of the molten zone near the pulled crystal; Controlling the section of the crystal using mechanical means, e.g. shaping guides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
- Y10S117/90—Apparatus characterized by composition or treatment thereof, e.g. surface finish, surface coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
- Y10T117/10—Apparatus
- Y10T117/1024—Apparatus for crystallization from liquid or supercritical state
- Y10T117/1032—Seed pulling
Definitions
- This invention relates to silicon single crystal pulling devices such as crucibles or dies made of silicon nitride and method of manufacturing the same.
- CZ Czochralski
- silicon is melted in a container (for instance a crucible), and a cylindrical single crystal of silicon is pulled up by rotating a seed crystal.
- the silicon melting container used in this CZ method is usually made of quartz glass.
- silicon and quartz glass are reacted with each other even at a temperature about equal to the melting temperature of silicon, and oxygen is trapped in the melted silicon. Therefore, about 2x10 18 atoms/cm 3 of oxygen is included in the single crystal silicon.
- the oxygen included in silicon precipitates to cause various crystal defects to deteriorate the crystal properties of the silicon single crystal.
- this single crystal silicon is processed to produce a semiconductor device, the electric properties thereof are extremely deteriorated.
- Prior art document Journal of Crystal Growth, volume 50, No. 1, September 1980, pages 347-365 discloses a method for producing a CVD silicon nitride layer containing 80% a-phase and 20% P-phase.
- a heat treatment of the CVD layer at 1200-1500°C causes formation of a-phase which then converts gradually to p-phase.
- the exposure of the CVD surface to molten silicon is sufficient to accelerate this conversion.
- the (3-phase content can be increased by controlling the deposition temperature.
- the CVD silicon nitride layer is extremely smooth so that maximum surface roughness is below 30 pm.
- CVD silicon nitride layers containing at least 80% a-phase are equally known from document Duffy et al., Report No. DOE/JPU954901-79/6 published by U.S. Department of Energy, December 1979.
- silicon nitride for melting silicon because of the fact that silicon nitride difficultly reacts with silicon.
- silicon nitride there are porous silicon nitride obtainable by a reactive sintering process and high density silicon nitride obtainable by a hot press process.
- polyvinyl alcohol or the like is used as a binder
- MgO, AIN, Y 2 0 3 or the like is used as a sintering promoter. This binder or promoter is inevitably introduced as impurity into the sintered silicon nitride.
- the inventors have conducted further researches and investigations on the basis of the above knowledge and have found that since silicon nitride produced by the CVD method has high purity, it is possible to obtain single crystal silicon, which has a high purity, a very low oxygen concentration less than 2 ⁇ 10 16 atoms/cm 3 and satisfactory crystal properties, by appropriately selecting various conditions for the pull-up of silicon single crystal in the CVD (chemical vapor deposition) process.
- the invention accordingly, has an object of providing a silicon single crystal pull-up device such as crucible or die, which is suited for the pull-out single crystals of silicon which has a high purity, with the oxygen concentration being less than 2x10 16 atoms/cm 3 and satisfactory crystal properties.
- Another object of the invention is to provide a method of manufacturing silicon single crystal pull-up devices as mentioned above.
- the present invention provides a device suitable for use in an apparatus for producing silicon single crystal from molten silicon, at least a portion of said device being in contact with said molten silicon, wherein at least a part of the portion of the device in contact with the molten silicon is comprised of a layer of silicon nitride precipitated on a refractory base member from gaseous phase, comprising at least 80% of a-phase whose crystal grains have grain diameter of 5 pm or above at a ratio of at least 10%, and having a smooth surface with the surface roughness of not more than 400 pm in Hmax, said device being characterized in that said base member includes as impurities less than 250 ppm of iron, less than 50 ppm of copper, and has a porosity in the range of 10 to 40%, and said silicon nitride layer contains as impurities not more than 3 ppm of boron, not more than 5 ppm of aluminum, and not more than 10 ppm of iron.
- the invention provides a method of manufacturing a device comprising a silicon nitride layer to be contacted with molten silicon when producing silicon single crystal or ribbon-like tin plate silicon crystal from the molten silicon, said silicon nitride layer comprising at least 80% of a-phase whose crystal grains have grain diameters of 5 ⁇ m or above at a ratio of at least 10%, wherein a crystalline silicon nitride layer is deposited at a temperature ranging from 1050 to 1450°C on at least the inner or outer surface of a refractory base member of a predetermined shape containing as impurities less than 250 ppm of iron, less than 50 ppm of copper, and having a porosity in the range of 10 to 40%, the crystalline silicon nitride layer deposited containing as impurities not more than 3 ppm of boron, not more than 5 ppm of aluminum, and not more than 10 ppm of iron by the CVD process, and then the deposited surface of the crystal
- the present invention is directed to the use of a device for producing silicon single crystal from molten silicon, at least a portion of said device being in contact with said molten silicon, wherein at least a part of the portion of the device in contact with the molten silicon is comprised of a layer of silicon nitride precipitated on a refractory base member from gaseous phase, comprising at least 80% of a-phase whose crystal grains have grain diameters of 5 ⁇ m or above at a ratio of at least 10%, and having a smooth surface with the surface roughness of not more than 400 pm in Hmax, the invention being characterized in that said base member includes as impurities less than 250 ppm of iron, less than 50 ppm of copper, and has a porosity in the range of 10 to 40%, and said silicon nitride layer contains as impurities not more than 3 ppm of boron, not more than 5 ppm of aluminum, and not more than 10 ppm of iron.
- the content of the P phase is set to be 20% or above because of the fact if the 13 phase is reduced to be less than 20%, other crystal phases such as a phase are increased so that the properties of the P phase, the reactivity of which with respect to melted silicon is extremely low compared to the a phase, are lost. In this case, ready production of reaction by-products is prone, making it difficult to obtain the pulling of desirable silicon single crystal.
- highly pure silicon single crystal can also be obtained with silicon nitride of not only ⁇ phase but also of a phase provided the crystal grain size is comparatively large.
- silicon single crystal of high quality as mentioned above can be obtained by using a pulling device for producing silicon single crystal from melted silicon by the pulling process using a seed crystal, in which part of silicon nitride to be contacted with the melted silicon contains at least 80% or above of a phase precipitated from gaseous phase and at least 10% of the crystal grains having lengths of no less than 5 p.
- the content of the a phase (crystal phase) is set to be 80% or above, because of the fact that if the a phase is below 80%, the quantity of non-crystalline silicon nitride is increased to increase the reactivity with the melted silicon, thus making difficult the pull-up of silicon single crystal having the intended crystal properties.
- the diametrical dimension and volumetric content of such a dimension the single crystal grains in the silicon nitride are respectively set to 5 p or above and 10% or above, because of the fact that if otherwise the number of crystal grains per unit area is increased to increase the reactivity with the melted silicon at the grain interface. For instance, even with the a phase system the edges of crystal grains are eroded and rounded although to a lesser extent than with the non-crystalline system. For this reason, it is difficult to obtain silicon single crystal having the intended crystal properties and purity by the pulling process.
- the silicon nitride as the material of the container according to the invention is manufactured by the CVD method, which permits ready refinement by raw material gas and also with which super-high purity can be achieved.
- the nature of the product material can be changed by finely controlling the conditions for manufacture, and the characteristics of the product silicon nitride can be varied by varying the deposition temperature and the composition of the raw material gas. More particularly, when the deposition temperature is within a range between 800 and 1,000°C, the product is non-crystalline silicon nitride, permitting no diffraction peak to be obtained by X-ray diffraction.
- the deposition temperature when the deposition temperature is in a range between 1,050 and 1,450°C, dense crystalline silicon nitride can be obtained. If the deposition temperature exceeds 1,450°C, many crystal grains deposited on a base member from gaseous phase grow in the form of vertical needles on the surface of the base member, and those which grow along the surface of the base member and tied to one another are reduced in number. It has been found that a loose structure, i.e., porous silicon nitride, results. For the above reasons, the deposition temperature as one of the conditions of the CVD process of depositing silicon nitride is set to be between 1,050 and 1,450°C, whereby silicon nitride of satisfactory properties as described above can be obtained.
- what results from depositing of a predetermined thickness of silicon nitride on at least either one of the inner and outer side of a base member having a predetermined shape by the CVD process may be directly used as the high density silicon nitride container, die or the like for pulling up silicon single crystal.
- a predetermined thickness of silicon nitride on at least either one of the inner and outer side of a base member having a predetermined shape by the CVD process may be directly used as the high density silicon nitride container, die or the like for pulling up silicon single crystal.
- Si 3 N 4 the sole deposited silicon nitride
- the material of the base member are carbon, silicon, silicon carbide and silicon nitride.
- the porosity is 10 to 40%, preferably 20 to 30%
- the Fe content is 250 ppm or below, preferably less than 150 ppm
- the Cu content is less than 50 ppm or below, preferably less than 10 ppm. If the Fe and Cu contents are above the aforementioned limits, the purity of silicon single crystal is reduced at the time of the pulling thereof due to these impurities. Also, polycrystallization is prone.
- the reason for setting the porosity of the sintered base member to be between 10 and 40% is that if it is below 10% the silicon nitride film deposited from gaseous phase is less close contact with the sintered body so that the peel-off of the silicon nitride film is prone, while if it is above 40% a rough silicon nitride film results from precipitation from gaseous phase so that pinholes are liable to be generated.
- the specific gravity of carbon based on the n-butylalcohol process is 1.30 to 1.60 g/cc and that the air permeability thereof is 10- 6 cm 2 /sec. or below.
- the range of the specific gravity of the carbon base member by the n-butylalcohol process is set as above without definite ground, but if this range is departed, inferior spalling-resistivity of the deposited film results.
- the air permeability of the carbon base member is set to the aforementioned range because of the fact that if it exceeds 10- 6 cm 2 /sec., the uniformity of the base member is deteriorated, and the number of open pores on the surface is increased. Consequently, projections of the deposited silicon nitride that fill the open pores at the interface with the base member are increased and remain as the source of thermal strain, giving rise to thermal cracks in the thermal cycle.
- the carbon base member may be removed to obtain a structure consisting of the sole silicon nitride; or the structure including the carbon base member without being removed may be directly used, as mentioned earlier.
- the silicon crystal base member either a polycrystalline silicon base member or a single crystalline silicon base member may be used.
- the polycrystalline silicon base member may be produced by molding silicon powder into a desired shape by a suitable molding method such as injection, rubber press or ordinary press and sintering the molding in an inert gas atmosphere at a temperature of 1,100 to 1,350°C.
- the silicon powder used may be what is obtained pulverizing semiconductor grade polycrystalline silicon or rejected semiconductor silicon single crystals or what is obtained by pulverizing byproducts in the silicon industry or in the manufacture of semiconductor grade polycrystalline silicon.
- a halogen compound of silicon or silane is used as a source of silicon and NH 3 , N 2 or the like is used as a source of nitrogen.
- the gas for suitably diluting these gases for transporting them i.e., carrier gas, H 2 or N 2 gas or a mixture gas thereof may be used.
- the thickness of the silicon nitride film according to the invention is desirably 5 p or above. The reason for this is that if the thickness is below 5 p, generation of local pinholes is liable, and such pinholes will cause intrusion of melted silicon into the silicon nitride body at the time of the pulling of the silicon single crystal, thus reducing the purity of the silicon.
- the boron content is 3 ppm or below
- the aluminum content is 5 ppm or below
- the iron content is 10 ppm or below.
- the heat-resisting base member on which the silicon nitride film is deposited need not be removed if there is no problem. However, if it is necessary to remove the base member, it may be selectively removed by making use of the difference in the physical or chemical properties between it and the deposited silicon nitride film.
- the carbon base member it is possible to obtain ready removal of carbon through oxidation.
- the silicon crystal base member it may be removed by various means such as by heating with HCI or C1 2 gas or melting it with the temperature thereof increased to above 1,417°C, the melting point of silicon, by increasing the temperature of high frequency heating in the CVD device after the deposition of the silicon nitride layer is ended.
- the silicon crystal base member may be removed without need of cooling down the deposited polycrystalline silicon nitride to the normal temperature but substantially at the same temperature as at the time of the deposition.
- the thickness of the silicon thin film is desirably set to 10 to 300 p. The reason for this is that if the thickness of the silicon thin film is less than 10 p, generation of pinholes is prone, causing the silicon nitride layer deposited on the silicon layer to be in contact with the base member thereunder through the pinholes.
- the silicon thin film may have a thickness in excess of 300 p, in this case a long time is required for its removal, which is undesired from the standpoint of the productivity.
- the base member may be repeatedly used, if the base member is hardly etched when removing the silicon thin film to separate the silicon nitride layer.
- the reason for holding the temperature in the series of steps of depositing the silicon thin film, depositing the silicon nitride layer and removing the silicon thin film in the range between 700 and 1,600°C is that if the temperature is below 700°C, not only the tendency of generation of thermal stress due to the coefficient of thermal expansion between the base member and silicon nitride film is increased but also the removal of the silicon thin film with the etching gas becomes difficult. On the other hand, if the temperature exceeds 1,600°C, the nature of the silicon nitride layer is adversely affected. A more preferred temperature range is 1,200 to 1,450°C.
- the surface roughness of the silicon nitride film is related to the degree of crystallization of silicon being pulled. More particularly, if the surface roughness of the silicon nitride film is increased, the area of silicon nitride in contact with the melted silicon is increased to increase the reactivity of silicon nitride and melted silicon with respect to each other, thus increasing the nitrogen concentration in the melted silicon.
- the surface roughness of the contact surface of the silicon nitride film in contact with the melted silicon is 400 p or below, preferably 25 u or below in Hmax, in any portion.
- Surface roughness, herein referred to as Hmax is determined by measuring the surface roughness of a crucible according to the rules of JIS B 0601.
- an Hmax of 400 ⁇ m means in this specification that 90% or more of the measured portion have exhibited surface roughness of less than Hmax 400 pm as prescribed in the JIS B 0601. This in turn may indicate that 90% or more of the total inner surface area of the crucible is less than Hmax 400 pm as prescribed in the JIS B 0601.
- the surface roughness of the silicon nitride film is adjusted to be in the aforementioned range by means of mechanical processing or etching or by suitably selecting the conditions of deposition of the silicon nitride film such as deposition speed, deposition temperature, deposition process, etc.
- the mechanical processing may be polishing with diamond.
- the etching process may be physical etching using sand blast or chemical etching using HCI gas, C1 2 gas, HF-HN0 3 , and etc.
- the depositing conditions it is possible for reducing the surface roughness to cause deposition from gas containing silicon and gas containing nitrogen at a temperature of 1,050 to 1,450°C or to set a low deposition speed as small as possible, for example preferably 1 to 40 um/hour.
- the orientation of the opening of the base member may be suitably selected when carrying out the deposition of silicon nitride to prevent adhesion of silicon nitride particle formed in the gases through the opening so as to smooth the surface roughness of the silicon nitride film.
- directing the opening in the horizontal direction or downwards or in a direction making a suitable angle, for instance 50°, from the upward direction so that no particles substantially fall into the inside has an effect of preventing the increase of the surface roughness.
- the surface roughness of the silicon nitride surface may be controlled by making smooth the outer or inner surface of the heat-resisting base member, depositing the silicon nitride film on the smooth outer or inner surface and then separating the heat-resisting base member and deposited silicon nitride film such that the surface of the deposited silicon nitride film having been in contact with the heat-resisting base member is submitted to in contact with the melted silicon.
- the contact surface of the silicon nitride film as a smooth surface conforming to the smoothness of the outer surface of the base member.
- the surface of the deposited silicon nitride film in contact with the heat-resistant base member is constituted by crystal grains of a very small grain diameter compared to the crystal grains of the outer side.
- High purity silicon powder was molded with polyvinyl alcohol used as binder. The molding was then subjected to a nitrifying process in a nitrogen atmosphere at 1,400°C for 5 hours to produce a porous crucible-shaped silicon nitride sintered body (base member).
- This base member contained 200 ppm of Fe and 40 ppm of Cu as impurities.
- the base member was put into a deposition furnace, and a crystalline silicon nitride film with a thickness of 80 to 130 ⁇ and mainly consisting of the (3 phase was deposited on the base member by the CVD process with 270 cc/min of SiCI 4 gas, 0.1 cc/min of TiC1 4 gas, 2,000 cc/min of H 2 gas and 80 cc/min of NH 3 gas supplied to the furnace and under pressure and temperature conditions of 200 Torr and 1,400°C, thus obtaining a silicon single crystal pulling crucible.
- Crystalline silicon nitride films with thicknesses of 80 to 130 p and mainly consisting of the a phase having a crystal grain of less than 20 ⁇ m are deposited on the base member of the above Example 1 in a deposition furnace under the same conditions as in the Example 1 except for that the TiCI 4 gas is not used, thus obtaining silicon single crystal pulling crucibles.
- the crucibles obtained in the Example 1 and Reference Example 1 and also a crucible consisting of reactive sintered silicon nitride (Comparison Example 1), a crucible consisting of hot press silicon nitride (Comparison Example 2) and a quartz glass crucible (Comparison Example 3) were used to melt and grow silicon by pulling a seed crystal from the surface of the melted silicon while rotating the seed crystal.
- the oxygen content and crystal state of the resultant cylindrical silicon products are as in Table 1 below.
- the character of silicon nitride film is listed in the columns for the Example 1 and Reference Example 1 and the character of silicon nitride is listed in the columns of the Comparison Examples 1 and 2.
- silicon single crystal could be obtained irrespective of the proportions of the a and P phases in the silicon nitride film.
- silicon single crystal could be obtained more readily with less reaction product produced in case of the crucible having the silicon nitride film containing much ⁇ phase (Example 1) compared to the case with the crucible having the silicon nitride film containing much a phase (Reference Example 1). This is thought to be due to the fact that the (3 phase silicon nitride is superior in stability at high temperatures and has extremely lower reactivity with respect to the melted silicon.
- the oxygen content is below 2x10 16 atoms/cm 3 , which is far lower than the oxygen of 1 ⁇ 10 18 atoms/cm 3 of the silicon single crystal obtained with the quartz glass crucible (Comparison Example 3).
- High purity silicon powder was molded with polyvinyl alcohol used as binder. Then, the molding was subjected to a nitrifying treatment in a nitrogen atmosphere at 1,400°C for 5 hours to obtain a porous crucible silicon nitride sintered body (base member). Then, such base members were used to produce four different silicon single crystal pulling crucibles by deposition of silicon nitride films with thicknesses ranging from 100 to 200 ⁇ m on these base members in a deposition furnace by the CVD process with 260 cc/min of SiCI 4 gas, 2,000 cc/min of H 2 gas and 80 cc/min of NH 3 gas supplied under a pressure of 20 Torr and at temperatures listed in the Table 2 below.
- the oxygen content in the silicon single crystals obtained by using the crucibles No. 7 and No. 9 was less than 2x10 16 atoms/cm 3 .
- silicon nitride films with a thickness of 280 p were deposited on the base members by setting the base members in a deposition furnace and supplying 260 cc/min of SiC1 4 , 80 cc/min of NH 3 gas and 2,000 cc/min of H 2 gas under a pressure of 20 Torr and at a temperature of 1,380°C.
- a commercially available electrode carbon material was prepared as the carbon base member for deposition. It has properties as shown in Table 4. Its bulk density was 1.7 g/cc, and its coefficient of thermal expansion was 3.0 ⁇ 10 -6 /°C. Silicon nitride films are deposited on this base member under the same condition as in the above Example 4, and the same sudden heating sudden cooling tests were conducted on the resultant test pieces. The results are also shown in Table 4.
- the spalling-resistivity is excellent with the composite system and also with the sole silicon nitride.
- Silicon single crystal or silicon polycrystal was pulverized with a carbonated tungsten mortar to prepare silicon powder with a grain diameter less than 150 meshes. Then, about 3% by weight of 0.5% solution of polyvinyl alcohol was added to the silicon powder. The mixture thus obtained was used to produce a crucible-like molding with a density of 55 to 65%, an outer diameter of 80 mm, an inner diameter of 72 mm and a height of 150 mm by the rubber press process. Then, the molding was sintered in an argon atmosphere at 1,200°C for about 3 hours to obtain a silicon polycrystalline base member. At the time of the sintering, this base member was contracted by about 6.0% so that the density was about 80%, the outer diameter was 75 mm, the inner diameter was 68 mm, and the height was 142 mm.
- the aforementioned crucible-like silicon polycrystalline base member was set on a support member of a CVD reaction apparatus such that the opening of the base member faced a gas inlet. Then, the base member was exhausted with a rotary pump by rotating the support member at a speed of 5 to 6 rotations per minute. Subsequently, H 2 gas was supplied at a rate of 2 I/min from the inlet while continuing the exhausting. At the same time, a carbon susceptor provided in the device is caused to generate heat by energizing a high frequency coil, for heating the silicon polycrystalline crystal base member with the heat of radiation until the surface thereof reaches 1,360°C.
- deposition of silicon nitride on the base member was carried out for about 15 hours by supplying 270 cc/min of SiC1 4 , 60 to 90 cc/min of NH 3 and 1,000 cc/min of H 2 gas toward the inner surface of the base member while maintaining the total gas pressure inside the device to be 25 to 30 Torr.
- a polycrystalline silicon nitride layer with a thickness of about 1.2 mm is deposited on the inner surface of a the crucible-like silicon polycrystalline base member.
- the supply of the SiC1 4 gas, NH 3 gas and H 2 gas is stopped, and the temperature inside the device is lowered to about 850°C, and the silicon polycrystalline base member was removed by dispersion by supplying HCI gas to obtain a crucible consisting of the sole polycrystalline silicon nitride.
- the silicon nitride crucible has a high purity and a high density. Also, the generation of local thermal stress was less, and the spalling-resistivity was excellent. This crucible was used to melt silicon and pull up a seed crystal from the surface of the melted silicon while rotating it, whereby a cylindrical silicon single crystal with a very low oxygen content of less than 2x 1016 atoms/cm 3 was obtained.
- Silicon powder was pulverized in an oscillating mill to obtain fine powder of a 325 mesh (Japanese Industrial Standards) pass or below. The fine powder was then washed several times with diluted hydrochloric acid several times to remove iron, alkali and others, and then the resultant fine powder was sufficiently washed with deionized water. The purified silicon fine powder thus obtained was then added to the deionized water containing NH 4 0H as deflocculating agent, and the resultant system was kneaded to prepare a slip with a pH of 8 to 9.
- Japanese Industrial Standards Japanese Industrial Standards
- the slip was then cast into a crucible-like gypsum mold to produce a round bottom crucible-like molding with a wall thickness of 3 to 7 mm, an outer diameter of 60 mm and a depth of 130 mm.
- the molding thus obtained had a density of 1.65 g/cc (corresponding to a silicon density of 70%) after natural drying. Thereafter, the molding was sintered in an argon atmosphere at 1,200°C for about 2 hours to obtain a crucible-like silicon polycrystalline base member with a density of about 85%.
- the aforementioned crucible-like silicon polycrystalline base member was set on a support member of a CVD reacting device such that its round bottom portion faces the inlet, then the temperature of the base member surface was elevated to 1,330°C by energizing a high frequency coil, and then deposition of silicon nitride was carried out for about 20 hours by supplying 300 cc/min of SiC1 4 and 85 to 95 cc/min of NH 3 through adjustment of corresponding needle valves and adjusting the flow of H 2 gas such that the total gas pressure is 20 to 30 Torr.
- a polycrystalline silicon nitride layer with a thickness of 1.8 mm was deposited on the outer surface of the crucible-like silicon polycrystalline base member. Thereafter, the supply of SicI 4 gas, NH 3 gas and H 2 gas was stopped, and the temperature inside the device was reduced down to 800°C. Then, the silicon polycrystalline base member was removed by supplying HCI to obtain a crucible consisting of sole polycrystalline silicon nitride and having a wall thickness of about 1.8 mm, an outer diameter of 60 mm and a height of 130 mm.
- the silicon nitride crucible thus obtained has a very high purity and a high density. Also, little local thermal stress was generated, and the spalling-resistivity was excellent. This crucible was used to melt silicon and pull up a seed crystal from the surface of the melted silicon while rotating it, whereby a cylindrical single crystal with a very low oxygen content of less than 2x 10 16 atoms/cm 3 could be obtained.
- a plate-like silicon crystal base member with a width of 50 mm, a length of 85 mm and a thickness of 1 mm is set upright in a CVD reacting device by inserting a 50-mm side of the base member in groove (about 2 mm deep) in a support member. Then, the device is exhausted while rotating the support member at a rate of 5 to 6 rotations per minute, and then H 2 gas is supplied at a rate of 2 I/min from the inlet while continuing exhausting. At the same time, the high frequency coil is energized to cause heat generation of a carbon heat generator in the device to heat the silicon single crystal with the heat of radiation until the temperature of the surface becomes 1,370°C.
- deposition of silicon nitride was effected for about 8 hours by supplying 230 cc/min of SiCl 4 , 75 cc/min of NH 3 and H 2 gas such that the total gas pressure is 25 to 35 Torr through adjustment of the individual needle valves.
- a polycrystalline silicon nitride layer with a thickness of 0.8 mm was deposited on the entire surface of the base member except for the portion thereof embedded in the support member.
- the system was taken out and set in a separate furnace (at a temperature of 900°C), and then HCI gas is supplied to the furnace to remove the exposed portion of the silicon single crystal base member not covered by the silicon nitride layer, thus obtaining a hollow silicon nitride body having an opening with a width of 1 mm and a length of 50 mm. Thereafter, the silicon nitride body was cut along planes parallel to the plane of the opening to obtain frame-like dies with a thickness of 0.8 mm.
- the crystalline silicon nitride die thus obtained was placed on the same silicon nitride crucible as that used in the previous Example 5, and melted silicon within the crucible was pulled through a hollow section of the die by using a ribbon-like seed crystal. In this case, no clogging due to reaction product to reaction between the die and melted silicon was resulted even for a period of use beyond 12 hours.
- the same die could be used for six times for pulling up ribbon-like silicon crystals with a thickness of 1.3 mm and a width of 50 mm and having a very low oxygen content of 2 ⁇ 10 16 atoms/cm 3 or below.
- Semiconductor polysilicon was pulverized, and the silicon powder thus obtained was molded with polyvinyl alcohol used as binder. The molding was then subjected to a nitrifying treatment in a nitrogen atmosphere at 1,400°C for 5 hours and then subjected to a purifying treatment in a C1 2 gas at 1,400°C, thus obtaining a base member.
- Such base members were used to produce silicon single crystal pull-up crucibles by introducing these base members into a deposition furnace and depositing a silicon nitride film with a thickness of 80 to 130 p on the entire base member surface by the CVD process by supplying 260 cc/min in of SiCl 4 , 2,000 cc/min of H 2 gas and 80 cc/min of NH 3 gas under a pressure of 20 Torr and at a temperature of 1,380°C.
- each crucible was used to melt silicon and produce silicon single crystal by pulling up a seed crystal from the surface of the melted silicon while rotating it. The results are shown in Table 5.
- the B content is preferably 3 ppm or below
- the AI content is preferably 5 ppm or below
- the Fe content is preferably 10 ppm or below.
- the comparison crucible shown in the Table is a crucible consisting of sole silicon nitride obtained by the prior art method of depositing a silicon nitride layer with a thickness of 500 ⁇ m on the inner surface of the crucible-like carbon base member under the same conditions as mentioned above, then taking the system out of the reaction furnace and cooling it down to room temperature and then removing the carbon base member through oxidation in an oxidizing atmosphere at a temperature of 500 to 1,000°C.
- Silicon single crystal pulling crucibles were produced in the manner as described in the Example 9, and their inner surface was machined using diamond powder to different surface states as shown in Table 7. These crucibles were used to conduct silicon pulling tests, and it was found that there is a relation between the surface roughness of the crucible and the degree of crystallization of silicon.
- the surface roughness of the silicon nitride film based on the CVD process is related to the speed and temperature of deposition of the silicon nitride.
- Table 8 shows the results of experiments conducted in connection to the relation among the deposition speed, deposition temperature and surface roughness.
- Table 8 shows the ratio (%) of the number of 10 mmx10 mm inner surface portions of each crucible made of silicon nitride which exhibited a roughness below 400 ⁇ m to the number of 10 mmx 10 mm inner surface portions of the crucible which exhibited a roughness of 400 pm or more, when measured in accordance with .the rules of JIS B 0601.
- a crucible base member similar to that in the Example 9 was produced, and deposition was carried out by setting the crucible opening orientation to various angles from the direct downward position (0°), and the surface roughnesses obtained with these angles and their effects were measured. The results are shown in Table 9.
- the crucible type A represents crucibles, in which silicon nitride is deposited on the outer wall surface of the base member such that the deposition surface is in contact with the melted silicon
- the crucible type B represents crucibles, in which silicon nitride was deposited on the inner wall surface of the base member such that the outer deposition surface is in contact with the melted silicon.
- the main reason for the polycrystallization occurring during the course of the pulling is thought to be due to a large area of contact with the melted silicon of the base member which exudates into the melted silicon and is reacted to result in the dissolution of the reaction product in silicon being pulled up, thus precipitating as P-Si3N4 on the surface-of melted silicon at low temperature to float and be trapped at solid-liquid interface and also trapped into the silicon being pulled to so as to constitute nuclei of crystal defects.
Claims (16)
Applications Claiming Priority (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56070477A JPS57188493A (en) | 1981-05-11 | 1981-05-11 | Manufacture of jig for pulling up silicon |
JP56070479A JPS57188409A (en) | 1981-05-11 | 1981-05-11 | Manufacture of high density silicon nitride |
JP7047481A JPS57188495A (en) | 1981-05-11 | 1981-05-11 | High density silicon nitride-base container for pulling up silicon single crystal |
JP70474/81 | 1981-05-11 | ||
JP70476/81 | 1981-05-11 | ||
JP70477/81 | 1981-05-11 | ||
JP56070478A JPS57188408A (en) | 1981-05-11 | 1981-05-11 | Manufacture of high density silicon nitride |
JP7047681A JPS5950626B2 (ja) | 1981-05-11 | 1981-05-11 | シリコン単結晶引上げ用容器 |
JP70475/81 | 1981-05-11 | ||
JP70479/81 | 1981-05-11 | ||
JP56070475A JPS5932427B2 (ja) | 1981-05-11 | 1981-05-11 | シリコン単結晶引上げ用高密度窒化珪素質容器 |
JP70478/81 | 1981-05-11 |
Publications (2)
Publication Number | Publication Date |
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EP0065122A1 EP0065122A1 (de) | 1982-11-24 |
EP0065122B1 true EP0065122B1 (de) | 1990-02-07 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP82103457A Expired - Lifetime EP0065122B1 (de) | 1981-05-11 | 1982-04-23 | Vorrichtungsteil aus Siliziumnitrid zum Ziehen von einkristallinem Silizium und Verfahren zu seiner Herstellung |
Country Status (3)
Country | Link |
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US (1) | US4515755A (de) |
EP (1) | EP0065122B1 (de) |
DE (1) | DE3280107D1 (de) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
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GB2188854A (en) * | 1986-04-09 | 1987-10-14 | Philips Electronic Associated | Apparatus and a method for growing a crystal using a low-pressure Czochralski method and a crucible holder for use in such apparatus and method |
US4911896A (en) * | 1986-07-24 | 1990-03-27 | General Electric Company | Fused quartz member for use in semiconductor manufacture |
US5268063A (en) * | 1990-04-27 | 1993-12-07 | Sumitomo Sitix Co., Ltd. | Method of manufacturing single-crystal silicon |
JPH0412083A (ja) * | 1990-04-27 | 1992-01-16 | Osaka Titanium Co Ltd | シリコン単結晶製造方法 |
JP3004563B2 (ja) * | 1995-04-20 | 2000-01-31 | 三菱マテリアル株式会社 | シリコン単結晶の種結晶 |
WO1998035075A1 (de) * | 1997-02-06 | 1998-08-13 | Bayer Aktiengesellschaft | Mit siliciumschutzschichten versehene schmelztiegel, ein verfahren zum aufbringen der siliciumschutzschicht und deren verwendung |
US5993902A (en) * | 1997-04-09 | 1999-11-30 | Seh America, Inc. | Apparatus and method for extending the lifetime of an exhaust sleeve for growing single crystal silicon by silicon nitride (SI3 N4) coating |
FR2774509B1 (fr) * | 1998-01-30 | 2001-11-16 | Sgs Thomson Microelectronics | Procede de depot d'une region de silicium monocristallin |
US6838047B2 (en) * | 2001-08-28 | 2005-01-04 | Romain Louis Billiet | MEMS and MEMS components from silicon kerf |
NO317080B1 (no) * | 2002-08-15 | 2004-08-02 | Crusin As | Silisiumnitriddigler som er bestandige mot silisiumsmelter og fremgangsmate for fremstilling av slike digler |
US20040211496A1 (en) * | 2003-04-25 | 2004-10-28 | Crystal Systems, Inc. | Reusable crucible for silicon ingot growth |
US20060051670A1 (en) * | 2004-09-03 | 2006-03-09 | Shin-Etsu Chemical Co., Ltd. | Non-aqueous electrolyte secondary cell negative electrode material and metallic silicon power therefor |
DE102005032790A1 (de) * | 2005-06-06 | 2006-12-07 | Deutsche Solar Ag | Behälter mit Beschichtung und Herstellungsverfahren |
CN101495681A (zh) * | 2006-06-23 | 2009-07-29 | Rec斯坎沃佛股份有限公司 | 用于生产半导体级硅的装置和方法 |
NO20092797A1 (no) * | 2009-07-31 | 2011-02-01 | Nordic Ceramics As | Digel |
CN103288357B (zh) * | 2013-06-20 | 2016-03-30 | 天津英利新能源有限公司 | 氮化硅溶液及其制备方法、多晶硅铸锭用坩埚及其制备方法 |
Family Cites Families (9)
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JPS6047202B2 (ja) * | 1976-01-13 | 1985-10-21 | 東北大学金属材料研究所長 | 超硬高純度の配向多結晶質窒化珪素 |
DE2632614A1 (de) * | 1976-07-20 | 1978-01-26 | Siemens Ag | Vorrichtung zum ziehen eines einkristallinen koerpers aus einem schmelzfilm |
US4090851A (en) * | 1976-10-15 | 1978-05-23 | Rca Corporation | Si3 N4 Coated crucible and die means for growing single crystalline silicon sheets |
JPS6031583B2 (ja) * | 1978-02-13 | 1985-07-23 | 株式会社神戸鋳鉄所 | 鋼塊用鋳型等の修理方法 |
JPS54157779A (en) * | 1978-06-02 | 1979-12-12 | Toshiba Corp | Production of silicon single crystal |
JPS5930645B2 (ja) * | 1978-11-08 | 1984-07-28 | 東ソー株式会社 | 高純度α型窒化珪素の製造法 |
JPS55113603A (en) * | 1979-02-19 | 1980-09-02 | Toshiba Corp | Manufacture of alpha silicon nitride powder |
JPS5845177B2 (ja) * | 1979-03-09 | 1983-10-07 | 富士通株式会社 | 半導体表面絶縁膜の形成法 |
JPS5913442B2 (ja) * | 1980-01-11 | 1984-03-29 | 東ソー株式会社 | 高純度の型窒化珪素の製造法 |
-
1982
- 1982-04-14 US US06/368,440 patent/US4515755A/en not_active Expired - Lifetime
- 1982-04-23 EP EP82103457A patent/EP0065122B1/de not_active Expired - Lifetime
- 1982-04-23 DE DE8282103457T patent/DE3280107D1/de not_active Expired - Lifetime
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DE3280107D1 (de) | 1990-03-15 |
US4515755A (en) | 1985-05-07 |
EP0065122A1 (de) | 1982-11-24 |
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